THE  ACTION  OF  PHENYLARSINE  ON  ALDEHYDES 


BY 


CHARLES  SHATTUCK  PALMER 
B.  S.  University  of  Illinois,  1917 
M.  S.  University  of  Illinois,  1920 


THESIS 


Submitted  in  Partial  Fulfillment  of  the  requirements  for  the 

Degree  of 


DOCTOR  OF  PHILOSOPHY 
IN  CHEMISTRY 

IN 


THE  GRADUATE  SCHOOL 


OF  THE 


UNIVERSITY  OF  ILLINOIS 


1921 


Digitized  by  the  Internet  Archive 
in- 2015 


) . L ,. 


https://archive.org/details/actionofphenylarOOpalm 


UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 

j.'joveiiioer  j , j 921_ 

I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 

SUPERVISION  BY CHARLES  SHAT  TUCK  PALMER 

ENTITLED  THE-  -A££I  Qli-QE  -PHBiiYXAESX^SL-QII-  ALDEHYDES.  ___ 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 
THE  DEGREE  OF Doctor  of  Philosophy 


Recommendation  concurred  in* 


Committee 

0)1 

Final  Examination* 


’Required  for  doctor’s  degree  but  not  for  master’s 


. 


*■  ; -1 


■ 


TABLE  OF  CONTENTS 

Page 

I.  INTRODUCTION:  PRIMARY  ARSINES  1 

Historical  1 

Preparation  of  arsines  2 

Reactions  of  arsines  2 

Sources  of  difference  between 

arsines  and  amines  4 

II.  THEORETICAL  5 

Previous  aldehyde -arsine  condensations  5 

Condensation  products,  C6H5As(CHOHR) s 6 

1,4, 3, 6 Dioxdiarsines  ? 

Reductions,  etc,  8 

New  Mechanism  of  arsine-arsine  oxide 

reaction  9 

III.  EXPERIMENTAL  11 

General  11 

Phenylarsinic  acid  11 

Phenyl arsine  13 

Analytical  14 

Condensation  products,  C6H5As (CHOHR) s 15 

Reactions  of  C6E5As (CHOHR)  5 21 

1,4, 3, 6 Dioxdiarsines  29 

Reactions  of  1,4,3, 6 dioxdiarsines  33 

Reduction  reactions  35 

Hydro  gen- chlorine  substitutions  40 

IV.  SUMMARY  41 


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m ■ 1 . 


- 1 - 

PART  1 
INTRODUCTION 
Primary  Arsines. 

Until  comparatively  recently  it  was  a fixed  belief  that 
arsenic  differed  from  nitrogen  and  phosphorus  in  that  primary 
and  secondary  arsines  were  incapable  of  existence.  Because  of 
the  extreme  rapidity  with  which  arsines  are  oxidized  by  air, 

(D 

many  attempts  to  prepare  such  substances  had  resulted  in  failute. 

It  was  not  until  1894  that  the  first  secondary  arsine,  dimethyl- 
(3) 

arsine,  (CH3)sAsH,  was  obtained  by  the  reduction  of  cacodyl 

chloride.  This  important  discovery  was  followed  seven  years 

(3) 

later  by  the  isolation  of  primary  arsines.  Possibly  on  account 

of  the  inconvenience  attending  the  handling  of  such  compounds, 

they  have  not  been  thoroughly  investigated  during  the  succeeding 

twenty  years.  The  application  which  arsenicals  have  found  in 

medicine  and  in  chemical  warfare  has  led  to  a resumption  of 

activity  in  this  interest ing  f ield.  The  work  reported  in  the 

following  pages  consists  in  reactions  which  take  place  when 

phenylarsine  is  treated  with  aldehydes  or  other  substances 

possessing  a similar  chemical  behavior  toward  amines.  According 

to  the  results,  striking  differences  between  aniline  and  its 

arsenic  analogue  have  been  found  to  exist. 

~(1)  M ichael  is,  A .201 , 304  (i860);  Michael  is,  Schulte,  B.15, 

1953  (1883);  Michael  is.  A . 330  , 276  (1902). 

(2)  Palmer,  B.27T  1378  (1894). 

(3)  Palmer,  Dehn,  B._34,  3594  (1901) 


. 

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* 

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* 

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- 2 - 


Theoretically  the  preparation  of  phenylarsine  closely 

resembles  that  of  aniline; 

C6H5As02  + 6H *■  C6HsAsH2  +■  3 H20 

In  practice  the  corresponding  arsonic  acid,  C6H5As03H2,  is 

reduced*  The  reduction  is  usually  carried  out  by  means  of  a 

(1)  (3) 

metal  and  mineral  acid,  but  may  be  done  electrolyt ically 

with  success.  All  primary  arsines  are  prepared  by  this  general 

method*  Only  the  first  three  members  of  the  series  of  aliphatic 

arsines  are  known*  The  synthesis  of  aromatic  arsines  has  been 

confined  mainly  to  such  substances  as  3-amino“4~hydroxyphenyl- 

arsine,  or  p -phenyl glycine  arsine,  which  are  comparatively 

stable  in  air  and  are  related  to  the  therapeutically  important 

salvarsan,  etc.  Such  arsines  have  a trypanooidal  action  about 

equal  to  that  of  the  arseno  compounds,  but  are  slightly  more 
(3) 

toxic. 

The  principal  reactions  of  primary  arsines  are  described 
below; 

1.  They  are  rapidly  oxidized  in  air  to  RAsO,  RAs-AsR, 

(4) 

or  RAs03H2 

2RAsH2  4 0 g RAs-AsR  +•  3H20 

RAsH2  +•  02  *-  RAsO  + H20 

RAsH2  4-  1 -l/302 ^RAs03H2 


(1)  B.34,  3594  (1901);  Am.  33,  101  (1905);  D.R.P,  251,571; 
Sieburg,  Ar,  254.  224  (1916)  . 

(2)  B.  34,  3594  (1901);  D.R.P,  267,  083;  270,658. 

(3)  Kahn,  Chem*  Ztg.  1913.  1099. 

(4)  B.  j34,  3597,3599  *11901);  Am.^33,  124,144,149  (1905); 

Am.  40,  115  (1908) . 


: 

. 

. 

, 

■ , 

. . 


...  . 

. ' . 

. . ; . . . . : 

_ . 

. 


- 3 - 

(1) 

2.  Inorganic  oxidizing  agents  have  a similar  action* 

The  following  are  the  most  important  examples: 

RAsHg  +■  2Kg0g — RAsO  + 3H20. 

RAsHg  + 6HN0  2 - RAs03Hg  f 3H20  + 6N0 

RAsHg  + 3N02 ^RAs03Hg  + 3N0 

5RAsHg  +•  6 KMn04 •- 3RAs03K2  + 2RAs03Mn  4-  4MnO 

+■  5H  gO 

3.  With  halogens,  sulphur,  HsS,  or  compounds  containing 

(2) 

active  halogen,  the  hydrogen  of  the  arsine  is  replaced. 


RAsHg 

4- 

^ 2 

RA s 1 2 +-  Hg 

RAsHg 

+ 

2S 

^RAsS  + HgS 

RAsHg 

4 • 

HgS  — 

— »*RAsS  + 2Hg 

RAsHg 

+ 

SnCl4- 

*-  RAsClg  +•  2SnClg 

RAsHg 

4- 

SgCl 2— 

RAsClg  4-  S + HgS 

4.  When  heated  with  alkyl  halides,  the  arsines  yield 

(3) 

quaternary  arsonium  compound si 

RAsHg  * 3CgH6I yR(C2H5)3AsI  + 2HI . 

5.  Primary  arsines,  condense  with  RAsO,  RAsCl2,RSbClg, 

K antimonyl  tartrate,  and  As,  Sb,  Bi  halides  with  formation 

(4) 

ol  arseno  compounds: 

RAsHg  4-  R’AsClg RA s=A sR 1 2 3 4 + 2HC1 . 

RAsHg  + R’AsO RAs=A sR*  + H20 


(1)  Am.  23,  125,  144,  149  (1905);  Am.  40,  105  ff  (1908) 

(2)  Am.  _33,  126,  150  (1905);  Am.  40,  105  ff  (1908) 

(3)  Am.  33,  128,  145,  152  (1905);  Am.  40,  112  (1908) 

(4)  Am.  40,  108  (1908);  D.R.P.  254,  187;  269,  744;  269,  745; 
270,  259. 

Ehrlich,  Karrer,  B.  46,  3564  (1913). 


• 

• 

. 

. a-  * 


. 


: 


; i } 

. • • 


- 4- 


RAsH2 

4- 

R«SbCl2- 

j-RAs-SbR' 

4-  2HC1 

RAsH2 

¥ 

SbBr3 

RAe=SbBr  + 

2HBr 

RAsH2 

+■ 

BiBr3 

—+•  RAs=BiBr  + 

2HBr . 

The  only  evidence  pointing  to  salt-forming  properties 

of  primary  arsines  is  the  formation  of  an  addition  product 

(1) 

between  ethylarsine  and  sulphuric  acid,  but  it  is  very  un- 
stable and  was  not  analyzed* 

An  extended  comparison  of  amines,  phoschines  and  arsines 

(3) 

already  exists  in  the  literature. 

Careful  consideration  of  the  foregoing  discussion  dis- 
closes three  principal  sources  of  difference  between  the  re- 
actions of  arsines  and  amines: 

1.  The  arsines  are  strong  reducing  agents. 

2.  The  basicity  of  the  arsines  is  practically  neg- 
ligible, 

3.  The  hydrogen  bound  to  arsenic  is  readily  exchanged 
for  halogen  or  sulphur. 

These  conclusions  have  been  confirmed  and  strengthened  in  course 
of  the  present  investigation. 

It  will  be  observed  that  little  has  been  done  in  comparing 
the  purely-  organic  reactions  of  the  arsines  with  the  amines. 

It  was  with  this  object  in  view  that  the  action  of  aldehydes  on 
phenylarsine  has  been  studied. 

(1)  Am.  33,  144  (1905) 

(2)  Dehn,  Am,  J33,  101-117  (1905) 


a - 

, ...... 


. ' .:  . . 

: 

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V 

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t . , f ) 


~ 5- 
PART  II* 
THEORETICAL 


Tne  first  indication  in  tne  .Literature  ox  an  attempt  to 

condense  an  aiaenyde  with  a primary  ar3ine  is  tne  inc±u3ion 

by  Dehn  of  formaldehyde  in  a list  of  substances  wmcn  did  not 

U) 

react  with  gaseous  metnyiarsme  • A little  later  the  conden- 
sation of  3-amino-4-hydroxyphenylarsine  with  benzaiaenyde-m- 

(3) 

su.iphonic  acid  is  described*  In  tnis  case  tne  ammo-group 

alone  reacted.  The  aoove  are  tne  only  examples  where  direct 

condensation  has  been  attempted.  Of  interest  in  this  connection 

is  the  compound  obtained  oy  treating  3-am ino -4- hydro xyphenyl- 

arsine  in  dilute  hyarocnlorio  acid  solution  with  an  excess  of 

(3) 

sodium  f ormal deny desulphoSCy late,  HO .GHB.0.80Ha  at  30®. 

From  tne  sulphur  content  of  the  product  it  appears  possible 
that  the  sulphoxylate  has  reacted  with  the  -AsH2  group  as  with 
an  amine, by  splitting  out  water.  It  is  uniortunate  that  in- 
sufficient information  is  given  so  that  a definite  conclusion 

as  to  tne  constitution  cannot  be  drawn. 

(4) 

Recently  it  has  been  found  that  .two  molecules  of 
aldehyde  react  witn  one  molecule  oi  phenyl&rsine  in  the  presence 
of  HG1  or  ZnOlg  as  catalyzer  according  to  the  following  equation:! 
C 6H5AsHg  + 3 RCHO *-  G 6H  BA  s ( CHOKR)  2 


(1)  Am.  40,  108  (1908) 

(2)  D.R.P.  373,035  (1913) 

(3)  D.R.P.  378,648  (1814) 

(4)  Am,  Soc.  43,  3375  (1920) 


6 


No  exactly  analogous  derivatives  of  phosphines  or  amines  are 

known*  Ammonia  and  benzaidenyde  combine  at  -20®  to  form  the 

(1) 

addition  compound,  NH(uri0HC6Hs) 2,  m.p.  45®.  Tftis  substance 

decomposes  very  readily  into  hydrobenzamide , benzaldehyde  and 

water.  When  treated  with  benzoyl  chloride  in  alkaline  solution, 

a little  benziiiaine-aibenzamide , C6rt5Ch(NHu0C6hs) 2,  is  formed. 

Phosphine  unites  with  two  molecules  of  cmcral  or  butyryl  chior- 

(3) 

al.  The  products  are  stable  solids,  which  yield  di-esters 

when  heated  witn  acetic  or  propionic  anhydride. 

Tne  condensation  products,  C6heAs(CHOhR) 2,  are  colorless 

oils  of  high  boiling  point,  or  colorless  needles.  They  possess 

a decided  stability  toward  water,  dilute  acids  and  dilute 

in 

alkalis.  This  behavior  is/str iking  contrast  to  that  of  the  iso- 

(3) 

meric  esters  of  phenylarsenious  acid,  C6H5As(0R)2.  Toward 
oxidizing  agents,  halogens,  phosphorus  pentachloride,  dimethyl 
sulphate,  the  condensation  products  act  like  mixtures  of 
phenylarsine  and  aldehyde.  With  phenyl hydrazine , acid  chlor- 
ides or  anhydrides  (in  the  cold)  reducing  agents  and  dehydrating 
agents,  no  action  is  observed.  Highly  unstable  addition  prod- 
ucts are  formed  by  allowing  the  aliphatic  condensation  products 
to  stand  with  constant  boiling  halogen  acid.  No  such  addition 
compounds  were  obtained  from  the  products  of  the  interaction 

of  phenylarsine  with  aromatic  aldehydes.  Stable  addition 

(1)  Francis,  B.  42,  2216  (1909) 

(2)  Girard,  C.r.  102,1113;  A.  ch.  (6)  2,  43  (168©)- 

(3)  Michael  is,  A.  J320,  286  (1902) 


7 - 


compounds  with  HgClg  and  chlorplat inic  acid  were  obtained  from 
both  aliphatics  and  aromatics.  Attempts  to  prove  hydroxyl 
groups  by  means  of  phenyl  isocyanate  and  the  Grignard  reagent 
gave  negative  results.  The  former  reagent  produced  decomposi- 


tion, while  magne  3 ium /iodide  had  no  effect  whatever.  In  spite 
of  the  lack  of  very  positive  proof,  the  formula  C6H5As  (CHOER)  2 
seems  the  safest  to  advance. 

When  heated  with  acetyl  chloride  or  acetic  anhydride,  two 
molecules  of  di-  -hydroxy  tertiary  arsines  lose  two  molecules 
of  alcohol  with  the  production  of  1,4, 3, 6 dioxdiarsines : 


Paraformaldehyde  and  furfural  yield  these  ring  compounds  directly 
the  first  type  of  condensation  product  being  unstable  in  these 
two  instances.  If  agitation  is  not  employed,  acetaldehyde  and 
phenylarsine  may  be  condensed  mainly  to  the  ring  compound,  the 
reaction  given  above  taking  place  as  an  intermediate  3tage. 

The  dioxdiarsines  are  much  higher  boiling  than  the  substances 
from  which  they  are  derived,  as  might  be  expected.  They  resemble 
the  latter  in  most  chemical  properties,  but  do  not  add  halogen 
acid.  The  addition  compounds  with  HgClg,  HgPtCl6  and  CuCl8  are 


methyl 


.O-CHR 

CeHsAs^ 

x RCH-0 


/sC6Hb  + RCE2OH 


stable 


- 


■ 


. 


, 

- 

* 


- 8 - 

The  dioxdiarsine s are  oxidized  by  atmospheric  oxygen  to 

phenylarsine  oxide  and  the  respective  aldehyde.  This  behavior 

differs  from  that  of  the  other  type  of  sub  stance , from  which 

phenylarsinic  acid  is  formed.  The  oxidation  of  dioxdiarsines 

(1) 

may  be  represented  as  follows: 


.O-CKR 

CgHgAs-s.  AsC6Hs  + Og 

RCH  - CT 


0 s ^ s A S_ 


SCH' 


0 


>AiC-H 


0^ 

0* 


6ll& 


2 C6H5AsO  t 2 RCHO 


From  analogy  with  aniline,  it  might  be  expected  that 
aldehydes  and  ketones  would  condense  with  phenylarsine,  when 
heated  together  with  dehydrating  agents,  according  to  the 
following  equation: 

~C~  0 + H2  AsC6H5- ^ =C=AbC6H5  + Hg0 

On  account  of  the  lack  of  basicity  of  the  arsines  and  their 
strong  reducing  properties,  a quite  different  reaction  takes 
place : 

2=C~0  + 2 CgHgAsHs *~2=CH0H  + C6HsAs=AsC6H6  . 

This  reduction  is  not  held  back  by  hydrochloric  acid,  since 
the  condensation  reactions  previously  described  are  entirely 
prevented  at  100© . 

(l)  Engler,  Weissberg:  "Kritische  Studien  iiber  die  Vcrgange 

der  Autoxiiation  (1904),  63,  Cf . Dehn,  Am.  40,  91ff  (19©8) ; 
Steinkopf,  Schwen,  B.  54,  1440  (1921). 


. 


- 


• r:  * . • 


. 


• : 

. 

: 


~ 9 ~ 

The  ease  with  which  halogen  is  substituted  for  hydrogen 
in  the  arsines  is  illustrated  by  the  action  of  chloral  on 
phenyl ars ine » The  aldehyde  group  does  not  react.  The  -CCi3 
group  attacks  the  phenylarsine  with  formation  of  phenylarsenious 
chloride,  C6H5AsC12. 

New  Theory  of  the  Reaction  between  Primary 

Aryl  Arsines  and  Aryl  Arsenious  Oxides  or  Halides. 

From  the  previous  discussion  it  appears  that  water  is  not 

split  out  between  the  carbonyl  group  = 0=0  and  the  primary 

arsine  group,  -AsH2»  The  fifth  general  reaction  in  Part  I 

indicates  the  elimination  of  water  between  primary  arsine  and 

arsine  oxide.  However,  thi3  reaction  can  be  explained  more 

satisfactorily  on  the  basis  of  the  reducing  rower  cf  the  arsine. 

The  arsine  reduces  the  arsine  oxide  to  an  arseno-compound,  and 

is  itself  oxidized  to  another  a r3e no-compound  in  the  process: 

2R ' AsO  + 2 RAsH2 ^R'As^AsR'  + RAs^AsR  + 2 Hg0 

The  rearrangement  of  two  arseno-compounds  into  the  unsymmetrical 

derivative  takes  place  very  smoothly  and  oractically  quant itat- 

(1) 

ively: 

R'As^AsR’  +■  RAs  = AsR *-3  RAs=AsR! 

Thus  exactly  the  same  product  is  obtained  as  by  the  assumption 
of  direct  condensation,  and  the  suggested  mechanism  is  strictly 
in  accord  with  experimental  results.  The  3arae  reasoning  applies 
to  the  interaction  tof  primary  arsines  with  arsine  halides, 

(l)D.R.P • 251104:  E .? . 17482:  Karrer,  B.49,  1648  (1916); 

D .R.P  . 253226;  2702S5. 


. 

. 

* 

. 

: ' 

. 

...  . . . 

... 


- 10 


stibine  oxides,  bismuth  tribromide,  etc. 

3 R'SbCls  + 3 RAsHs *-R'Sb«SbR'  + RAs-AsR  + 4 HC1 

R ' Sb=SbR ' + RA  s=A  sR *2  RAs=SbR  ' 


11  - 


PART  III 
EXPERIMENTAL 
General  . 

dr 

Phenylarsinic  acid,  C6H6As03H2»  - The  most  general 

method  for  the  preparation  of  aromatic  arsinic  acids  is  Bart’s 

(3) 

reaction  : 

R—  N — Cl  f As(ONa)  3 ^ RAs03Na3  + N2  * NaCl  „ 

N 

For  the  production  of  phenylarsinic  acid  on  the  large 
laboratory  acale,  a 25~1 . cylindrical  copper  tank,  provided 
with  mechanical  stirrer  was  employed.  In  the  tank  were  pierced 
4 1.  of  water,  2 kg.  Na2C03,  1 kg.  As203  (about  2C$excess), 
and  45  g.  copper  sulphate.  The  stirrer  was  started  and  the 
walls  of  the  tank  cooled  by  several  streams  of  water.  As  soon 
as  the  temperature  of  the  arsenite  solution  fell  to  15»,  the 
addition  of  diazo  solution  was  begun.  It  was  found  convenient 
to  prepare  the  latter  in  four  portions.  186  g.  aniline,  400  cc. 
cone.  HC1,  1 1.  water  and  sufficient  ice  to  bring  the  total 
volume  to  3 1.  were  placed  in  a 4-1  • Florence  flask.  This 
mixture  was  diazo tized  in  the  usual  manner  with  a concentrated 
solution  of  140  g.  NaNOa.  Three  hours  or  more  were  required 
for  running  four  of  these  solutions  into  the  arsenite,  the 
temperature  of  the  latter  being  maintained  at  15© . 

(1)  LaCoste,  Michaelis,  A.  201,  203,  (1880) j Michaelis,  Loesner, 
B.  27,  265  (1894);  Bertheim,  B.  41,  1855  (1908). 

(2)  D.R.P.  250,  264;  254092.  See  also  J.  Ind.  Eng.  Chem.  11, 

825  (1919);  Schmidt,  A.  421,  159  (1920) 


. i 

* 

. . ' i . 

; •*  . • 

. • 

* 

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• . : ' • ‘ . . ■ • 
......  . . ' : 


- 13  - 

Stirring  was  continued  for  1 hour  after  all  the  diazo  had 
been  added.  The  solution  was  filtered  and  the  filtrate  con- 
centrated to  a volume  of  approximately  5 1.  in  16  in.  evapor- 
ating dishes  on  the  steam  bath.  100-300  cc . cone.  HC1  were 
added  cautiously  and  the  tarry  material  filtered  off.  This 
process  was  repeated  until  a clear,  pale-yellow  solution  re- 
sulted. The  phenylarsinic  acid  was  then  precip itated  by 
addition  of  more  HC1,  avoiding  an  excess.  When  the  solution 
had  cooled,  the  product  was  filtered  off  and  washed  with  a 
little  distilled  water.  The  average  yield  of  white  or  cream- 
colored  product  exceeded  800  g.  (=  50 # of  the  theory) » Phenyl- 
arsinic acid  softens  at  158®  and  passes  into  its  infusible 

anhydride,  C6H6AsOs. 

(1) 

Phenylarsine,  C6H5AsHg. 

1.  Original  method  of  Palmer  and  Dehn. 

A 5-1.  round-bottom  flask  was  provided  with  a long  bulb 
reflux  condenser.  A 3-hole  stopper  at  the  upper  end  of  the 
condenser  carried  a 3-1.  dropping  funnel  and  an  outlet  tube 
connected  to  a mercury -f illed  U-tube . In  the  flask  was  placed 
a mixture  of  400  g.  phenylarsinic  acid  and  800  g.  amalgamated 
zinc  dust,  a little  water  and  1 1 . of  ether.  3 1.  cone.  HC1 
were  added  drop  by  drop;  by  proper  regulation  the  apparatus 
could  be  allowed  to  run  over  night  without  attention.  When 

(1)  B.  _34,  3598  (1901);  Am.  J33,  101  (1905);  Chem.  Ztg.  1913 , 

1099, 


:1  ; (. 

. 

• . 


. 

. 


■ 


- 13 


the  reduction  was  complete,  the  condenser  was  removed  and  re- 
placed by  a 3-hole  stopper  carrying  a 6 in.  funnel  and  a delivery 
tube.  By  pouring  water  into  the  funnel,  the  ether  layer  was 
forced  through  the  delivery  tube  into  a C02-filIed,  2-1.  sep- 
aratory funnel.  Lumps  of  anhydrous  CaCl2  were  added.  When 
dry,  the  solution  was  transferred  in  portions  to  a 500  cc.- 
C02-filled  Claisen  distillation  flask  fitted  with  a receiver 
of  equal  size  and  most  of  the  ether  removed  by  heating  on  the 
steam  bath,  a constant  current  of  C02  being  passed  through 
the  apparatus.  The  distillation  was  continued  under  diminished 
pressure.  By  a little  practice  it  was  found  possible  to 
change  receivers  without  oxidation  of  phenylarsine,  so  that  use 
of  a Bruhl  apparatus  is  unnecessary.  The  product  boiling  around 
93®,  70  mm.  was  collected.  When  the  distillation  was  completed, 
the  vacuum  was  shut  off,  C02  admitted  to  atmospheric  pressure 
and  the  product  sealed  in  large  test-tubes  which  had  been  pre- 
viously constricted  near  the  open  end,  and  filled  with  carbon 
dioxide.  The  best  yield  obtained  was  83%;  the  average  was 
nearly  60 Phenylarsine  is  a clear,  colorless  liquid  of  dis- 
agreeable odor.  It  causes  painful  blisters  when  it  comes  in 
contact  with  the  skin  and  is  highly  irritating  to  the  mucous 

membrane.  Constants  not  given  in  the  literature  are: 

25  25 

N,  1.6082.  Dgg,  1.356 

2.  Steam  distillation  method  of  Kahn. 

In  thi3  method  the  phenylarsine  was  removed  from  the  re- 


. 


J • 


♦ 


I , - 

. 

. . 

• r *1  - ••  . .. 

« ‘ * ‘ ^ i ■ . . •' 

. 

. 

. 

. 


- 14- 

action  mixture  by  simultaneous  streams  of  C02  and  steam*  The 
condenser  was  connected  to  a large  f liter-flask, cooled  in  a 
freezing  mixture.  The  outlet  of  the  receiver  was  joined  to 
a U-tube  containing  mercury  through  which  C02  and  excess  hydro- 
gen escaped.  Chemicals  were  employed  in  the  same  amounts  given 
in  the  first  method.  Although  this  procedure  is  comparatively 
rapid,  yields  are  no  better  and  phenylarsine  is  so  volatile 
that  all  of  its  vapor  is  not  condensed  even  by  use  of  a glass 
worm  surrounded  by  salt  and  ice.  Steam  distillation  is  better 
adapted  to  the  preparation  of  solid  arsines. 

Several  attempts  to  reduce  phenylars inic  acid  in  a manner 
analogous  to  the  commercial  preparation  of  aniline  »by  use  of 
iron  powder  and  a small  quantity  of  HC1  - were  unsuccessful. 

This  result  was  anticipated  on  account  of  the  more  ready  reduc- 
ibility  of  the  nitro-group.  Thus  nitro-arsinic  acids  may  be 

a) 

reduced  to  amino -are inio  acids  by  means  of  sodium  amalgam  or 

(2) 

ferrous  hydroxide. 

Analyt ical .-  For  carbon  and  hydrogen  determination  a 
combustion  tube  packed  with  pieces  of  a sintered  mass  contain- 
ing equal  weights  of  copper  oxide  and  lead  chromate  was  used. 
Ewins'  method  for  the  determination  of  arsenic  was  given  a 

(4) 

thorough  trial,  but  is  less  satisfactory  than  that  of  Robertson. 
All  As  determinations  given  below  were  done  according  to  the 
directions  of  the  latter  author. 

(1)  Bertheim,  B.41,  1657(1908);  D.R.P.  206344;  Bertheim,  Benda, 
B.44,  3299  (1911) 

(2)  Jacobs,  Heidelberger . Rolf,  Am.Soc.  40,  1580  (1918) 

(3)  Soc,  109,  1356  (1916) 

(4)  Am.  Soc.  43,  182  (1921) 


, - ' i : - . ■ 

•r 

. 

. 

. . . . ..'ir 

• ' : : •• 

• • ' o . ' 


,"t  . ■ •' 


. 

■ ’ ■>  . + .+  tr'V>  U i 

, . ... 


. . . : 

'i 

. 


- 15- 

Condensation  Products.  C6HBAs(CHOHR) 2 . 

Pi-  oc-  -hydroxyethylohenvlarsine . 

A 500  cc.  wide-mouth  bottle  was  provided  with  a mechanical 
stirrer  and  placed  in  an  ice-bath.  C02  was  passed  into  the 
bottle,  100  g.  phenyl arsine  and  3 cc.  cone.  HC1  poured  in  and 
the  stirrer  started..  75  g.  acetaldehyde  or  paraldehyde  (an 
excess)  were  added  drop  by  drop.  Stirring  and  the  C02-stream 
were  continued  for  an  hour  or  two  after  the  addition  of  the 
aldehyde  was  completed.  The  reaction  mixture  was  shaken  up 
with  a little  fused  K2C03,  which  served  to  remove  HC1,  phenyl- 
arsinic  acid  and  moisture,  and  then  distilled  under  diminished 
pressure.  The  yield  of  redistilled  product  boiling  at  175-176°/ 
23  mm.  was  137  g.  (=  81%  of  the  theory)  » Clear,  colorless  oil, 
Dgl  * 1.252;  n2^  = 1.5592.  Insoluble  in  water,  soluble  in 

organic  solvents. 

Subst.,  0.3637:  C02,  0.4743:  H20,  0.1430. 

Subst.,  0.1356,  0.1274:  10.2  cc.,  9.65  cc.  iodine  (l  cc . = 

.0041  g.  Asi 

Subst.,  0.6072:  Benzene,  22.0:  f .p  • lowering,  0.564°. 

Calc,  for  C^qHjqOjjAs:  C.  49.59:  H,  6.19:  As.  30.99:  Mol.  wt.  # 242. 
Found;  C.  49.03:  H,  6.02:  As.  30.83,31.05:  Mol.  wt.,  246. 

The  aliphatic  homologues  of  this  substance  resemble  it  in 
physical  and  chemical  properties.  All  of  the  condensation 
products  were  prepared  as  described  above,  except  that  stirring 
was  not  used  in  small  runs  and  in  some  cases  a solvent  was  em- 
ployed. Identical  yields  were  obtained  by  use  of  dry  HC1. 


. 

. 


. 


- 16  - 

Pi-  oi-hydroxypropylohenylarsine . - 17  g.  propionic  aide- 
hyde  and  23  g.  phenylarsine  were  condensed  in  the  presence  of 
HC1 « Yield,  70$. 

B.P.,  21  3-3140  /70  mm.  ; D§5,  1.176;  H35,  1.5310. 

Sub  at.,  0.2043:  13.8  cc.  iodine  (1  cc.  = .0041  g.  As) 

Calc,  for  CigHjgOgAs:  As,  27.77 
Found:  As,  27.69. 

(1) 

Di-  cl  -hydro  xybutylphenyla.r  sine  • * By  preparing  this  sub- 
stance in  the  same  manner  as  described  for  the  acetaldehyde 
condensation  product  it  was  obtained  in  75%  yields.  (75  g.  from 

50g.  phenylarsine  and  50  g.  butyryl  aldehyde.)  The  refractive 

(l ) 

index  was  reported  incorrectly  in  the  preliminary  paper. 

P r 25 

Corrected  constants  are:  B.P.,  187© /10  mm.;  Dg£,  1.116;  n'"", 

1.5271. 

Subst.,  0.2296,  0.2210:  14.0  cc . , 13.5  cc.  iodine  (l  cc.  = .0041  g. 
As)  . 

Calc,  for  C* 4H2302As:  As,  25.17 . 

Found:  As,  25.00,  25.05. 

Di-  cx  -hydroxvlsovalervlnhenylarsine » - 16  g.  isovaleryl 
aldehyde  were  allowed  to  react  with  15  g.  phenylarsine.  Yield, 
59$.  The  product  is  a rather  viscous  oil,  b .p  . 235© /36  mm., 

P25>  1*^79;  n25,  1,5172.  A small  portion  was  solidif ied .by 
immersion  in  a freezing  mixture . After  recrystallication  from 
ether,  needles  were  obtained  which  melted  sharply  at  62© . 

(1)  Am.  Soc.  42,  237  6 (1920) 


. 


. . 


. 


: ' 


. ' 


- 17  - 

Subst.,  0.1980:  11.1  cc . iodine  (l  cc.  = 0041  g.  As) 

Cal  c . for  CjgHjj^OgAs:  As*  23.8?  » 

Found:  A3,  uj2«98» 

Pi-  a:  -hydroxvheptylphenyl arsine  - ’Mien  oenanthol  was 
condensed  with  phenylarsine,  the  product  distilled  with  decomp- 
osition under  20  mm.  pressure  and  formed  an  agar-like  mass  when 
cooled  in  a freezing  mixture.  In  another  experiment,  15  g. 
oenanthol  and  6 g.  phenylarsine  were  condensed.  The  reaction 
mixture  was  dissolved  in  ether,  extracted  with  NaHS03  solution 
and  allowed  to  stand  over  night  in  contact  with  air  in  order 
tc  oxidize  any  free  phenylarsine  to  arsenobenzene , The  residue 
was  redissolved  in  ether,  filtered  and  the  purification  re- 
peated. The  final  ether  solution  was  dried  over  fused  K2C03  and 
evaporated.  Analysis  of  the  colorless  residual  oil  showed  the 
presence  of  somewhat  impure  oo,  oc'-dihydroxyisoheptylphenyl- 
arsine • 

Subst.,  0,1818:  8.1  cc,  iodine  (l  cc.  * .0041  g.  As) 

Calc,  for  CgQHggOjgAa:  As,  19.83. 

Found;  As,  16.2? 

Glucose --phenyl  arsine .-  All  attempts  at  obtaining  any 
reaction  between  glucose  and  phenylarsine  failed.  A consider- 
able number  of  experiments  were  carried  out  in  which  the  effects 
of  long-standing, heat ing,  solvents  and  mechanical  agitation 
were  observed.  In  every  case  the  two  substances  were  recovered 
practically  quantitatively. 


: 


. * . • 

1 ’ . w 

. 

' 


• • ... 

: 


. 

* 


- 18  - 

(1) 

Dl-  oc -hydroxybenzylphenylarsine  - 300  cc.  of  benzene, 

58  g.  benzaldehyde,  2 cc . cone.  HC1  were  placed  in  a wide -mouth 
bottle  of  one  liter  capacity  which  was  provided  with  a mechan- 
ical stirrer.  The  bottle  was  immersed  in  a bath  of  ice  and 
water,  the  stirrer  started,  C02  passed  in  and  40  g.  phenylarsine 
added.  Precipitation  began  almost  immediately;  after  15-20 
minutes  the  reaction  mixture  looked  like  whipped  cream.  After 
two  hours  the  product  was  filtered  off,  and  washed  thoroughly 
with  ether.  More  was  obtained  by  concentrating  the  combined 
filtrate  and  washings  to  small  volume.  The  whole  was  recrystal- 
lized from  hot  benzene  and  allowed  to  stand  over  night  in  a 
dilute  NaOH  solution  to  which  a little  alcohol  had  been  added. 

The  insoluble  material  was  filtered  off  and  washed  with  water , 
alcohol  and  ether.  In  this  way  a purer  product  was  obtained 
than  by  several  recrystallizations  since  in  the  latter  case  a 
trace  of  phenylarsinic  acid  persisted.  Yield,  65  g;,  colorless, 
silky  needles,  m.p.  193©. 

Sub st.,  0.1522,  0.1876;  C02,  0.3704,  0.4499;  H20,  0.0695,  0.0843. 
Subst.,  0.1740,  0.1505;  8.7,  8.5  cc.  iodine  (l  cc.  * .0041  g.  As) 
Subst.,  1.3709;  naphthalene,  26.73:  f.p.  lowering,  0.972©. 

Calc,  for  C2OH1902A8:  C,  65.58;  H.  5.19;  As,  20.66;  Mol.  wt . , 366 
Found:  C,  65770,  65.41;  H,  5.11,  5.01;  As,  20.47,  20.43:  mol.  wt . 

364 . 

Pi-  cc -hydroxy -p-chlorobenzylphenylarsine . - 9 g.  Eastman’s 
p-chloro- 

/benzaldehyde  were  dissolved  in  25  cc . of  acetone.  5 g.  phenyl- 
arsine and  0.5  cc . cone.  HC1  were  added  and  the  solution  allowed 

(1)  Am.  Soc.  42,  2377  (1920) 


c 


l 


- 19  - 

to  stand  over  night  in  a tightly  stoppered  C02-filled  flask. 

A slight  heat  effect  was  noticed  at  first.  To  isolate  the 
product,  the  reaction  mixture  was  evaporated  to  dryness,  the 
residue  extracted  with  alcohol  and  the  insoluble  portion  re- 
crystallized from  chlorobenzene.  Needles  similar  to  the  ben- 
zaldehyde  compound,  m.p.  160°.  Yield,  1-1/2  g. 

Subst.,  0.1057:  4.3  cc.  iodine  (1  cc.  - .0042  g.  As) 

Subst.,  0.1411:  A gCl , 0.0905. 

Calc,  for  C2qHj  yOgCl  2A  s : As,  17  .24;  Clj  16.48 

Found;  As,  17.08;  01,  16.65. 

Pi-  oc.  -hydroxy -n-methoxybenzyliphenylarsine .-  27  g.  anisic 
aldehyde,  15  g.  phenylarsine , 200  cc . ether  and  1 cc.  cone. 

HC1  were  placed  in  a 500  cc.  wide-mouth  bottle  and  the  reaction 
run  as  described  for  the  benzaldehyde  compound.  After  standing 
over  night,  the  solution  was  extracted  with  aqueous  bisulphite 
and  evaporated  to  dryness.  This  purification  was  repeated 
until  constant  composition  was  obtained.  The  final  product  was 
a yellow  syrup.  Yield,  33$. 

Subst.,  0.1835,  0.2013:  7.65,  8.5  cc . iodine  (l  cc,  = .0041g.  As) 
0 al c * for  C g gH g gO  4 A s : As,  17. 61 « 

Found:  As,  17.09,  17.31. 

Pi-  cc  -hydroxy-o-oxvacet icbenzyl -phenyl s.rsine  acid. 

o-Aldehydophenoxyacet ic  acid  was  prepared  by  the  method  of 

(1) 

Rossing.  It  was  purified  by  fractional  precipitation  from 
(1)  B.  17  , 3000  (188  4) 


J. 


- 20  - 

solution  in  dilute  NaOH.  30  g.  of  this  aldehyde  were  condensed 
with  13  g.  phenylarsine  in  the  usual  manner,  using  100  cc. 
acetone  for  solvent  and  1 cc.  cone.  HC1,  The  solvent  was  evapo- 
rated spontaneously  and  the  oil  which  remained  was  dissolved  in 
the  theoretical  amount  of  dilute  sodium  hydroxide.  After 
evaporation  of  the  water  at  room  temperature,  the  sodium  salt 
crystallized  in  a hard,  orange-brown  mass.  This  was  dissolved 
in  water  and  the  free  acid  precipitated  in  fractions  by  dilute 
HC1,  the  first  small  fractions  being  discarded.  The  remaining 
product  was  washed  several  times  by  decantation  with  distilled 
water  and  dissolved  in  just  enough  concentrated  NaOH.  On 
spontaneous  evaporation  the  salt  crystallized  in  purified  con- 
dition. It  was  transferred  to  a filter,  washed  with  acetone 
and  dried  in  vacuo  over  HgSO*.  The  final  product  is  yellow 
powder,  readily  sol\ible  in  water.  Yield,  8 6$. 

Subst.,  0.1574,  0.1941:  4.8,  5.8  cc.  iodine  (l  cc.=.0Q446g.  A3) 

Calc,  for  C g ^ Og A sNag : As,  1o»4*j. 
found:  A3,  13.59,  13.26. 

Pi-  <x  -hvdroxv -m -nit robe nzvlnhenyl arsine 18  g.  m-nitro- 
benzaldehyde , 1 cc . cone.  HC1,  50  cc.  ether  and  9 g.  phenyl- 
arsine were  placed  in  a tightly  stoppered,  C02-filled  Erlenmeyer 
flask.  The  mixture  became  quite  warm  and  the  m-nitrobenzalde- 
hyde  went  into  solution.  After  standing  over  night,  the  flask 
was  opened  and  a current  of  air  passed  through  the  solution 
for  one  hour  in  order  to  oxidize  any  phenylarsine  which  had 


- 21  - 


failed  to  react.  The  solution  was  then  extracted  several  times 
with  aqueous  sodium  bisulphite  and  evaporated  in  vacuo  over 
H2S04.  An  amber  glue,  weight  37  g.,  remained.  After  one  repeti- 
tion of  the  purification,  the  product  was  analyzed. 

Subst.,  0.1050,  0.2007:  4.7,  9.05  cc , iodine  (lcc  .*  .0041g.  As) 
Calc,  for  C2OHl706N2As:  As,  16.44 

Found:  As,  16.35;  18.01. 

After  another  purif ication  the  substance  was  analyzed  again. 

Subst.,  0.1165,  0.1977:  5.35,  8.9  cc.  iodine  (lcc .=.0041  g.  As) 

Found:  As,  18.67;  18.46. 

Several  runs  of  this  compound  were  made.  All  of  the  products 
contained  about  18$  of  arsenic.  It  is  possible  that  reduction 
of  the  nitro-group  occurred  at  least  partially,  though  only 
traces  of  arsenobenzene , the  oxidation  product  of  phenylarsine, 
were  recovered.  The  reduction  of  nitrobenzene  to  hydrazobenzene 
by  means  of  phenylarsine  is  described  under  the  heading 
"Reduction  Reactions." 

Reactions  of  the  Condensation  Products,  C6H5As(CHOHR)  2 . 

Heat.  When  the  condensation  products  were  heated  in  a 
test-tube  over  a free  flame,  they  were  decomposed  with  evolu- 
tion of  aldehyde.  A black  solid  was  formed  which  proved  to  be 
a mixture  of  triphenyl arsine  and  free  arsenic. 


3 C6H6As<CHOHR)2- 


6 RCHO  + (C6H5)3As  + 3 As  + 3 H2 


- 23  - 

Water*  The  products  were  Unchanged  after  long  standing 
under  water.  5 g.  of  the  butyryl  compound  and  25  cc,  of  water 
were  sealed  in  a bomb  tube  and  the  lower  end  of  the  latter 
immersed  in  an  oil  bath  heated  at  140°  for  30  hours.  At  the 
end  of  that  period  the  substance  was  unchanged.  In  a similar 
manner  1 g.  of  benzaldehyde  compound  was  recovered  unchanged 
in  weight  and  melting  point  after  65  hours’  heating. 

Dilute  sodium  hydroxide.  The  butyryl  compound  and  ben- 
‘•zaldehyde  compound  were  unchanged  after  24  hours  heating  at  140© 
with  10#  NaOH, 

Oxidation.  After  standing  for  ten  months  in  corked  test- 
tubes,  samples  of  the  propionic  and  isovaleric  compounds  had 
deposited  a white  sediment.  The  supernatant  liquid  contained 
one-fourth  less  arsenic  than  the  fresh  product  and  gave  a strong 
fuchsin  aldehyde  test.  The  solid  was  identified  as  phenyl - 
arsinic  acid.  Equation: 

C6H6As(CHOHR)s  + 3 0 *-C6H6As03H2  + 2 RCHO 

This  oxidation  is  more  rapid  in  solution,  particularly 
in  carbon  tetrachloride.  Thus  1 g.  butyryl  compound  was  dis- 
solved in  10  cc.  aldehyde -f ree  CC14  and  a slow  stream  of  air 
passed  through  the  solution  for  1 hour.  Heat  was  evolved,  the 
solution  became  turbid  and  the  odor  of  phosgene  was  very  distinct. 
The  mixture  gave  a strong  aldehyde  test  and  on  evaporation 
phenyiarsinic  acid  was  obtained.  No  action  was  observed  when 
C02  was  substituted  for  air.  The  same  results  were  given  by 
the  acetaldehyde  compound. 


. 

. 

. 

. 

. 

. 

. 


. 

: 

. 

. 

. 

- 

. 

. 


- 23  - 

5 g.  butryi  compound  were  placed  in  a 50  cc » Claisen 
flask  connected  to  a glass  worm  and  receiver,  both  cooled-  by 
ice  and  water.  16  cc.  35$HN03  were  added  through  a dropping 
funnel.  A vigorous  reaction  took  place.  The  distillate,  weight 
2 g.,  was  identified  as  butryi  aldehyde.  On  evaporation  of  the 
solution  remaining  in  the  Claisen,  2-3/4  g.  of  phenylarsinic 
acid  were  recovered. 

C6H5As(CHOHR)  s + 6 HN03- ^C6H5A303R2  * 2 RCHO 

+ 3 HgO  + 6 NO  2 . 

It  was  found  that  the  acetaldehyde  compound  is  oxidized 
to  aldehyde  and  phenylarsinic  acid  by  nitric  acid  or  alkaline 
permanganate . 

Reduction.  A number  of  attempts  were  made  to  reduce  the 
acetaldehyde  compound,  presumably  C6H5As(CHOHCH3) 2,  to  phenyl - 
diethylarsine,  C6H5A s ( CH2 . CH3) 2 . Zinc  and  HC1,  aluminium  powder 
and  NaOH,  zinc  and  glacial  acetic,  and  sodium  and  absolute  al- 
cohol did  not  produce  any  reduction,  the  original  substance 
being  recovered  in  each  case. 

Dehydration.  When  a solution  of  the  acetaldehyde  compound 
in  dry  ether  was  allowed  to  stand  over  P20B,  slight  charring 
occurred,  but  most  of  the  product  wa3  recovered  unchanged. 

Fused  ZnCl2  dissolved  in  the  same  compound  with  formation  of  a 
thick  glue,  probably  an  addition  product. 

Ten  grams  of  the  acetaldehyde  compound  and 


»! 


. 

' ' 

. ...  ■ 

* 

. 

. 

• - - r ’ ■ ' * < • i 

. . 

. 

. 

* 

. 

. 

. 


- 35  - 

C 6H BA s ( CHOHR)  2 t Clg ^CgHgAsClg.  + Hs  + 2 RCHO 

[cis 

C6H6AsC14 
I HgO 

C6HbAs03H3  + 4 HC1 

Halogen  acids . The  butyryl aldehyde  and  benzaldehyde 
compounds  were  stable  to  long  standing  with  dilute  HC1,  but 
decomposition  started  quickly  on  boiling.  Decomposition  also 
occurred  on  standing  or  boiling  with  concentrated  HC1.  Con- 
stand  boiling  HBr  had  a similar  action  on  acetaldehyde  phenyl- 
arsine  but  in  addition  to  the  decomposition  there  was  formation 
of  a yellow  solid,  apparently  an  addition  product.  The  acid 
was  decanted,  the  solid  boiled  with  alcohol,  filtered  off  and 
washed  with  ether.  Yellow  powder,  m.p.  117-116®,  insoluble  in 
water,  slightly  soluble  in  organic  solvents.  The  substance  is 
quite  unstable,  30on  melting  to  a pasty  mass.  In  a similar 
manner  constant  boiling  HI  formed  addition  compounds  with 
acetal dehyde-phenylarsine,  m.p.  94-96°,  and  butyryl  aldehyde- 
phenylarsine,  m.p.  157-158°.  These  are  more  unstable  than  the 
HBr  addition  compound  which  they  resemble.  Analysis  of  the 
acetal de hyde -phenyl a r sine -HI  compound  indicated  an  addition 
of  one  molecule  HI  to  one  of  ace taldehyde-phenylar sine • 

Subst.,  0.2187:  10.9  cc.  iodine  (l  cc.  * .00446  g.  As) 

Calc,  for  ClfiH1BOaAs.HI:  As,  20.37. 

Found:  As,  32.33. 


. 


. 


. 

• • , 

• . - . , ..t  ' TAP. II 

. • 

. . ' • I tlVt'  ■ 

' 


' ■.  . > T ' 2t .JCo 


. 

: . • 

. . ; ■; 


- 36  - 

Mercuric  chloride.  When  warmed  with  aqueous  mercuric 
chloride,  the  condensation  products  form  highly  insoluble 
solids.  The  solution  was  decanted,  the  solid  boiled  with 
alcohol,  filtered  off  and  washed  with  ether.  The  products 
are  stable  white  or  grayish  solids,  practically  insoluble  in 
water  and  organic  solvents.  They  decompose  without  melting. 
Analysis  of  the  substance  obtained  from  acetaldehyde-phenyl- 
arsine  indicated  addition  of  two  molecules  of  HgCl2. 

Subst.,  0.2616:  6.2  cc.  iodine  (l  cc.  * .0041  g.  As) 

Calc,  for  C1oHl60jAs  . 2 EgClgi  As,  9. 56$. 

Found:  As,  10,19$ 

Ethyl  iodide.  6 g.  butyryl  compound  and  4 g.  ethyl  iodide 
were  placed  in  a 100  oc.  round  bottom  flask  connected  to  a re- 
flux condenser.  After  20  hours  of  heating  on  the  steam  bath, 
the  solution  was  transferred  to  a crystallizing  dish  and  con- 
centrated. Only  phenylarsenious  oxide,  m.p.  122°,  could  be 
found.  The  same  result  was  obtained  with  the  benzaldehyde 
coiipound,  3 g.  acetaldehyde  compound  and  2 g.  ethyl  iodide 
were  sealed  in  a test-tube  and  allowed  to  stand  for  six  months. 
A dark  glue  was  obtained  which  could  not  be  purified. 

Phosphorous  pehtachloride . 35  g.  PG1S  were  treated  with 

20  g.  of  acetaldehyde  compound  in  a Claisen  flask  connected 
to  a glass  worm  condenser.  The  heat  of  the  reaction  was  ab- 
sorbed by  an  ice-bath  so  that  the  distillate  came  over  below 


. 

. 


. 

. 

. 


. 

. 


- 2?  - 

60° , It  consisted  of  acetaldehyde  mixed  with  a little  ethyli- 
dene  chloride  and  phosphorous  oxychloride,  weight  5 g.  The 
distillation  was  continued  in  vacuo.  A fraction  boiling  below 
60° /80  mm.,  weight  31  g.  consisted  mainly  of  F0C13.  The 
fraction,  153-155° /18  mm.,  weight  16  g.,  was  identified  as 
phenylarsenious  chloride. 

Subst.  0.2127:  11.0  cc.  iodine  (l  cc.  - 0.0064  g.  As) 

Subst.,  0.1663:  AgCl,  0.2173. 

Calc,  for  C6HsA3C12:  A3,  33.63:  Cl,  31.84. 

Found:  As,  33.57:  Cl,  32.29. 

C6H6As(CH0HH)2  f 2 PClg ^C6H6AsC12  + 2 HC1  + 2 P0C13 

+ 2 RCHO . 

On  account  of  its  low  boiling  point  most  of  the  acetalde- 
hyde escaped  before  it  could  be  acted  upon  by  the  PC16. 

Phenylarsenious  chloride.  1 g.  acetaldehyde  compound  was 
placed  in  a corked  test-tube  with  an  equal  weight  of  phenyl 
arsenious  chloride.  Slight  warming  and  turbidity  were  observed. 
After  one  week  the  mixture  was  practically  solid.  It  was 
transferred  to  a filter  and  washed  with  ether.  The  residue 
was  identified  as  araenobenzene , mixed  m.p.  196-199°.  The 
indicated  reaction  is: 

C6H6As(CH0HR)2  + C6HBAsCls ^CeH8As*AsC6H5 

4 2 HC1  t 8 RCHO. 

Acid  chlorides.  Many  attempts  were  made  to  prepare 
esters  from  all  of  the  simple  condensation  products  by  msans 
of  acetyl  chloride,  acetic  anhydride,  oxalyl  bromide,  benzoyl 


. 


♦ 


4 

* 

. 

... 

• 

, * 

. 

. 

. * . 

... 

. 

. 

. . 

- 28  - 

chloride  and  p -nit robe nzoyl  chloride.  In  the  cold  without 
solvent,  in  the  Schot ten- Baumann  reaction  and  in  pyridine 
solution,  the  compounds  were  unaffected.  The  result  of  heating 
certain  of  the  substances  with  acid  chlorides  or  anhydrides  is 
discussed  in  the  next  main  section. 

Dimethyl  sulphate.  1 g.  acetaldehyde  compound  and  3 cc. 
10$  NaOH  were  placed  in  a test-tube . Dimethyl  sulphate  was 
aided  with  constant  shaking  as  long  as  any  action  took  place. 

On  standing  in  air  the  non-aqueous  layer  crystallized.  This 
product  was  identified  as  arsenobenzene,  mixed  m.p.  196-300®. 
Apparently  the  dimethyl  sulphate  merely  splits  the  aldehyde- 
arsine  product.  No  attempt  was  made  to  determine  the  action 
of  dimethyl  sulphate  on  the  aldehyde. 

Orignard  reagent.  The  acetaldehyde  and  butyrvl  alde- 
hyde condensation  products  were  indifferent  to  the  action  of 
a large  excess  of  magnesium  methyl  iodide  in  dry  ether  solution. 
No  gas  was  evolved  after  several  weeks  standing  in  a fermen- 
tation tube.  By  decomposition  of  the  organo -metallic  compound 
with  water,  ether  extraction  and  vacuum  distillation,  the 
original  products  were  recovered  nearly  quantitatively. 

Phenyl 1 so cyanate . 5 g.  phenyl isocyanate  and  5 g.  acet- 

aldehyde compound  were  sealed  in  a bomb  tube.  A pink  solution 
formed  which  had  the  same  appearance  after  standing  over  night. 
The  tube  was  heated  for  30  hours  at  150°  . On  opening  a very 


* 


' 


. 


. 


. 

n . - ' 


. - 


* 


* 


- 29  - 

heavy  pressure  was  observed.  The  reaction  mixture  was  trans- 
ferred to  a filter  and  washed  with  ether.  The  residue  was 
recrystallized  from  nitrobenzene,  weight  5 g.  It  wa9  identi- 
fied as  diphenylurea,  mixed  m.p.  335°.  The  ether  filtrate 
was  evaporated,  leaving  a dark,  gluey  residue  which  contained 
31.7%  of  arsenic.  It  was  not  investigated  further.  Phenyl- 
isocyanate  had  a similar  action  on  the  butyryl  compound. 

Phenylhydrazine . The  acetaldehyde  compound  was  unchanged 
when  heated  for  several  minutes  in  a test-tube  with  an  excess 
of  phenylhydrazine  in  glacial  acetic  acid  solution. 

Condensation  products,  (C6H5) gAsgOs(CH) 2R2. 

- — — — ~ “ ” .O-CH  2 . 

3.6  Diphenyl.  1.4. 3. 6 dioxdiarsine , CfiHRA3v  ^ AsC6H5 

xCH2-0  " 

5 g.  paraformaldehyde  and  12  g.  phenylarsine  were  placed  in  a 
C02-filled  test-tube  and  0.5  cc.  cone.  HC1  added.  The  tube 
was  sealed  and  shaken  from  time  to  time  for  about  half-an-hour 
afterwards.  Heat  was  evolved,  the  paraformaldehyde  dissolved, 
and  a clear,  colorless  solution  resulted.  After  standing  over 
night  or  longer,  the  tube  was  opened  and  the  contents  trans- 
ferred to  a C02“*filled  Claisen  distillation  apparatus.  The 
fraction  which  came  over  below  110® /? 43mm.  contained  water, 

HC1  and  formaldehyde.  On  continuing  the  distillation  under 
diminished  pressure,  the  mixture  decomposed  with  loss  of  a 
low-boiling  substance.  No  constant  boiling  distillate  was 
obtained  until  21 4®/ 9 mm.  was  reached.  The  presence  of  methyl 


• '■<  . • '• 

* ' . . 

. . rf  * tjf, ' 

. 

* - • • * ■ \ .. 

-- .....  , 

i.  . . - . ..  1") 

. 

. 


*■  . s a *,  r 1 ' 

. 

■ - 

. 


- 30- 

alcohol  in  the  fraction  boiling  below  214®/ 9 mm,  was  shown 
by  the  preparation  of  methyl  3,  5 dinitrobenzoate  from  3,5 
dinit robenzoyl  chloride  and  0,5  cc,  of  the  liquid.  The  fraction 
boiling  at  214® -220®/ 9 mm,  was  collected  and  immediately  re- 
distilled. This  time  no  loss  of  volatile  substance  was  noted. 
The  final  product  is  a colorless,  viscous  oil  which  rapidly 
decomposed  in  the  air  and  must  be  preserved  in  C02-filled, 
sealed  test-tubes.  Yield,  8 g.  B.P.  215-216®/ 9 mm;  DgS,  1*547: 
n25,  1.6522.  Several  runs  were  made  in  an  attempt  to  obtain 
the  condensation  product,  C6H6As(CH20H)  2,  but  no  constant 
boiling  fraction,  other  than  stated  above,  could  be  obtained. 

It  seems  safe  to  conclude  that  dihydroxymethylphenyl-arsine 
was  formed  initially,  but  that  on  distillation  two  molecules 
of  methyl  alcohol  were  split  out  between  two  of  the  former 
substances,  a six-membered  ring  resulting. 

Sub st.,  0.2560:  C02,  0.4320:  H20,  0.0970. 

Subst.,  0.3953,  0.1617:  39.4,16.1  cc,  iodine  ( 1 cc ,0043g.As) 
Subst.,  0.7900:  22,0  g.  benzene:  f .p . lowering,  0.506®. 

Calc,  for  C14H1402As2:  C,  46.15:  H,3.85:  As,  41.21:  Mol.  wt . 

364: 

Found:  C,  46,01:  H,4.08,  As,  41.81,  41.82:  Mol.  Wt.  355. 

2.5  Dimethyl.  3.6  diphenyl.  1,4,3. 6 lioxiiarsine . 
^o-ch-ch3 
C6H6As^  \u  c6h6 
CH^CH-d7 

110  g.  phenylarsine  and  several  cc.  cone.  HC1  were  placed 
in  a C02-filled  500  cc.  Erlenmeyer  flask.  100  g.  paraldehyde 
(large  excess)  were  added  drop  by  drop  simultaneously  with  the 
passing  of  a current  of  dry  HCT1  into  the  reaction  mixture.  No 


- 31  - 

agitation  of  any  kind  was  employed*  After  1 hour  the  stream 
of  HC1  was  stopped,  the  flask  stoppered  tightly  and  allowed 
to  stand  over  night.  On  distillation,  59  g.  of  di-  <x  “hydroxy- 
ethyl  -phenvlarsine , B.P.  174-176°/  22  mm.,  were  obtained.  The 
residue  in  the  distilling  flask  was  dissolved  in  acetone,  the 
solution  filtered  and  the  acetone  allowed  to  evaporate.  There 
remained  a thick,  clear,  amber-colored  glue,  weight,  65  g. 

A portion  of  this  was  distilled  with  very  slight  decomposition 
at  257°/ 10  mm.  The  final  product  was  nearly  colorless. 

fc  pc 

1.369:  n^  , 1.6332.  It  is  much  more  stable  to  air  than 
the  formaldehyde  compound. 

Sub st.,  0.2158,  0.1478:  COg,  0.3913,  0.3638,  H20,  0.1000:0.0668. 
Subst.,  0.1786,  0.1577:  16.5,  14.6  cc . iodine  (lee  .* .0041g.As) 
Subst.,  0.5415:  23.0  g.  benzene:  f .p . lowering,  0.320°. 

Calc,  for  C16Hl802Ass:  0,  48.98:  H,  4.59:  As,  38,27:  mol.  wt. 

392, 

Found:  C, 48,98,  48.75:  H,  5.19,  5.06:  As,  37.88,  37.87:  mol. 

Wt.  384, 

24.  g.  di-  o c-  -hydroxyphenylarsine  and  10  g.  acetic  an- 
hydride were  placed  in  a wide  tube  connected  to  a worm  reflux 
condenser.  After  heating  for  7 hours  on  an  oil  bath  at  140-150°, 
the  mixture  was  distilled,  using  a fractionating  column. 

The  fraction  75-90°  gave  an  aldenyde  test  but  consisted  mainly 
of  ethyl  acetate.  The  distillation  was  continued  under  dimin- 
ished pressure  and  7 g.  of  the  ring  compound  obtained. 


- 32  - 


2,5  Dipropyl,  3.6  diphenyl.  1.4. 3, 6 dioxdiarslne . 
(CHS)*CH3 
,0-CH. 

CsH6A9<  >AsC6H6 
CH-0 

CHsfOH  ,)» 


5 g.  acetic  anhydride  and  15  g.  di-  CC  -hydro xybut yip he nyl- 
arsine  were  refluxed  for  6 hours.  The  mixture  was  distilled 
from  an  oil-bath  using  a fractionating  column.  The  fraction 
123-140°  was  insoluble  in  water,  had  a strong  ester  odor  and 
consisted  mainly  of  butyl  acetate,  although  it  gave  a fuchsin 
aldehyde  test.  Apparently  the  formation  of  aldehyde  was  due 
to  heat  decomposition.  The  distillation  was  continued  under 
diminished  pressure  and  the  product  which  had  not  distilled 
below  230° /8  mm.  was  retained.  It  was  dissolved  in  dry  ether, 
the  solution  filtered  and  the  ether  evaporated.  After  a repeti- 
tion of  this  treatment,  7 g.  of  an  amber  oil  were  obtained. 


Subst.,  0.1055,  0.1627;  8.7,  13.4  cc.  iodine  (lcc^.0041  g.As) 

Calc,  for  C2OH2602As2:  As,  33.48 
Found:  As,  33.81,  33.77. 

2,5  Djfurvl . 3.6  diohenyl.  1.4. 3,6  dloxiiarsine . 

28.  g.  freshly  distilled  furfural  and  1 cc.  cone.  HC1 

were  added  to  32.5  g.  phenylarsine  in  a C02-filled  bottle  in 

an  ice-bath.  A very  violent  reaction  took  place,  the  mixture 

turned  dark  and  sufficient  heat  was  evolved  to  crack  the  bottle,. 

On  cooling,  a hard  mass  like  a piece  of  coke  formed.  When 

powdered,  the  product  resembled  zinc  dust.  It  is  insoluble 

in  all  solvents  and  when  heated  on  a platinum  foil,  burns 


- 33 


without  melting,  leaving  no  residue*  The  powdered  substance 
was  treated  for  a few  minutes  with  boiling  benzene,  filtered 
off  and  dried.  After  a similar  extraction  with  dilute  alkali, 
the  compound  was  analyzed.  The  yield  was  quantitative. 

Subst.,  0.1898,  0.1206:  13.1,  8.3  cc . iodine  (1  cc .-.00446g.As) 

Found:  As,  3©. 78s  30.33. 

The  same  substance  was  obtained  when  furfural  was  added 
drop  by  drop  to  a vigorously  stirred  benzene  solution  of 
phenyl arsine  at  20© . 

Subst.,  0.2  5 57:  C02,  0.5214;  H20,  0.0879. 

Subst.,  0.1477,  0.1470:  7,05,7,  1 cc.  iodine  (lee .«.0064g.  As) 
Cal c . for  C g i g 0 4 A s 2 » 0 , 53.33;  H,  3.63:  As,  30  *34. 

Found:  C, 55.61:  H,  3.85:  As,  30.54,  30.90. 

Reactions  of  the  Pioxdiar3ines. 

Unless  otherwise  designated,  the  technique  for  the  work 
described  below  was  the  same  as  that  employed  for  the  corres- 
ponding reactions  of  the  compounds,  C6HsAs(CH0HR) 2 . 

Water,  dlli  HQ1,  dll»  NaOH.  The  methyl  compound  was  un- 
affected by  long  standing  with  these  rea]gents  in  the  cold.  A 
portion  boiled  for  three  hours  with  alcoholic  KOH  remained 
unchanged . 

Oxidation.  The  formaldehyde  ring  compound  is  very  rapidly 
oxidized  by  air.  17  g.  of  the  substance  were  dissolved  in  50  cc. 
of  acetone  and  the  solution  allowed  to  stand  in  the  air*  The 
mixture  warmed  up  and  gave  a very  strong  aldehyde  test*  After 


- 34  - 

standing  over  night  the  acetone  was  evaporated  and  the  residue, 
wei^it  ,16g. , recry  stall  ized  from  alcohol.  It  was  identified 
as  phenylarsine  oxide. 

Subst.,  0.1649*,  16.6  cc.  iodine  (l  cc.=.00446g.  As) 

Calc,  for  C6H5AsO:  As,  44.64. 

Found:  As,  44.89. 

The  methyl  and  propyl  compounds  were  oxidized  in  a similar 
manner  by  the  air,  but  the  action  was  very  slow, 

1 g.  methyl  compound  was  treated  with  cone.  HNQ3.  Aldehyde 
was  evolved  and  phenylarsinic  acid  obtained  by  evaporation .of 
the  remaining  solution. 

Reaction: 

(C6HbAsOCHR)s  4-  8 HN03 -2  C6H5As03H2  + 3 RCHO 

+ 8 JNO2  4-3H20 

Iodine . 1 g,  methyl  compound  was  dissolved  in  10  cc.  of 

ether  and  iodine  added  in  small  portions.  Aldehyde  was  evolved 
and  a dark  heavy  oil  formed.  It  was  washed  with  ether  by  de- 
cantation. Since  it  gave  free  iodine  and  phenylarsinic  acid  with 
cone.  HN03,  it  was  considered  to  be  C6H5AsI2. 

Halogen  acids.  Constant  boiling  halogen  acids  did  not  form 
addition  products  as  with  the  compounds  of  the  first  type.  Slow 
decomposition  took  place,  but  no  attempt  was  made  to  identify 
the  products. 


- 35  - 

Phosphorus  pentachloride , 1 g.  methyl  compound  was  treated 

with  excess  of  phosphorus  pentachloride.  Vigorous  reaction  and 
evolution  of  aldehyde.  The  reaction  mixture  was  treated  with 
water  cautiously  and  the  precipitated  oil  identified  as  phenyl- 
arsine  dichloride  by  a method  previously  described. 

Ethyl  iodide , 2 g,  methyl  compound  and  a considerable  ex- 

cess of  ethyl  iodide  were  refluxed  for  four  hours.  On  evaporation 
of  the  excess  ethyl  iodide,  the  original  ring  compound  was  recover- 
ed unchanged  and  practically  quantitatively. 

Metallic  Salts;  Addition  compounds  are  formed  with  HgClg, 
CuCls,  HjgPtClg,  but  not  with  ZnCl2,  CdCl2,  CaCl2.  To  0,5  g, 
methyl  compound  in  15  cc,  alcohol  was  added  an  excess  of  chlor^ 
platinic  acid.  After  shaking  a minute  or  two,  the  product  was 
precipitated  in  fractions  by  water,  washed  and  dried  on  a plate. 
White  powder, 

Sub6t.,  0,0980:  4,3  cc . iodine  ( lcc  .s=.00446g.  As) 

Subst.,  0.1685:  0,0385  g.  Pt . 

Calc,  for  Cl6Hl802As2HHsPt016:  As,  18.70;  Pt,  34.31. 

Found:  As,  19.55;  Pt,  22.85. 

Reduction  Reactions 

Aldehydes . 7,5  g.  phenvlarsine  and  5 g.  benzaldehyde 

were  dissolved  in  25  cc,  of  glacial  acetic  acid.  The  solution 
was  refluxed  in  a current  of  C02  for  two  hours.  The  precipitated 
solid  was  filtered  off  and  washed  with  ether.  It  was  identified 
as  arsanobenzene,  weight,  6.75  g.  This  and  many  other  samples 


36  - 


of  arsenobenzene  which  were  obtained  were  mixed  with  sufficient 
phenylarsinic  acid  to  cause  them  to  melt  high.  After  extraction 
with  alkali  and  one  or  more  recrystallizations  from  benzene  or 
chlorbenzene,  a melting  point  and  mixed  melting  point  of 
196-197®  was  found. 

Subst.  0.2466;  28.6  cc . iodine  (1  cc»=.0042  g.  As) 

Calc,  for  C12H1CiAss;  As,  49.33. 

Found:  As.  49.34, 

The  filtrate  from  the  arsenobenzene  had  a very  strong 

ester  odor.  On  distillation,  acetic  acid  was  recovered.  A 

fraction,  which  boiled  at  200-210®  under  atmospheric  pressure, 

was  refluxed  over  night  with  an  excess  of  strong  aqueous  NaOH. 

The  mixture  was  distilled,  the  non-aqueous  layer  removed  and 

identified  as  benzyl  alcohol  by  preparation  of  the  p-nitro- 

(1) 

benzoate,  m.p.  84-88®.  A portion  of  the  residue  which  remained 
in  the  distilling  flask  was  evaporated  to  dryness  and  the 
presence  of  acetic  acid  shown  by  the  cacodyl  test. 

2 C6H6CH0  4-  2 C6HsAsH2  + 2 CH3C00H 2 C6H5CHs00C  .CH3  + 

2 HgO  + C6HsAs=AsC6H6 

Phenylarsine  was  oxidized  similarly  when  heated  with  benzalde- 
hyde  in  1:1  proportion  in  a sealed,  C02-filled  tube  at  100®. 

The  reduction  took  place  even  in  the  presence  of  cone.  HC1 , the 
condensation  reaction  apparently  being  eiltirely  prevented  at 
100®  . 


(1)  B.  30,  2288  (1897) 


. 

. 

. 

• 

. . 4 

• • 

. 

* 

. 

. 

' 

, fc:  ‘ 

• 

• . . 


' 


' 


. 


* 


- 37  - 

29  g.  benzaldehyde , 20  g.  phenylarsine,  75  cc.  benzene 
and  a piece  of  ZnCls  were  allowed  to  stand  in  a C02-f  illed 
paraff in- sealed  flask.  After  5 days  the  flask  was  opened 
and  the  solid  material  filtered  off.  From  this  residue  were 
obtained  16  g.  arsenobenzene  and  3 g.  phenyl arsinic  acid.  The 
filtrate  was  distilled  and  10  g.  benzaldehyde  recovered.  The 
residue  from  this  distillation  was  recrystallized  from  alcohol 
and  pressed  out  between  filter  papers,  weight,  7g.,  m.p.  58-60®, 
This  corresponds  to  desoxybenzcin , but  the  mechanism  by  which 
this  product  could  be  formed  is  not  clear. 

9 g.  Eastman's  p -chi o robe nz aldehyde  and  10  g.  phenylarsine 
were  dissolved  in  75  cc . benzene,  1 g.  fused  ZnCl~  added  and 
the  mixture  allowed  to  stand  for  5 days  in  a CO  3-f  illed, 
sealed  flask.  No  condensation  took  place.  The  flask  was 
opened  and  arsenobenzene,  dry  weight,  10  g.,  filtered  off. 

On  concentration  of  the  filtrate,  long  prisms  were  obtained, 
m.p.  70® -71®  , weight,  9 g.  This  checks  for  p-chlorobenzyl 
alcohol  • 

Subst.  0.1216:  AgCl,  0.1258. 

Calc,  for  C7H7OCI : Cl,  24.84 
Found:  Cl,  25.59. 

2 C1C 6H6 .CHO+3  C6HbAsH3 -2  Cl ,C6H4 .CH30H  + 

C gH  5 A s—A  sC  gH  g 


* 


. 


. 


- 38  - 

27  g.  anisic  aldehyde  and  15  g.  phenylarsine  were  treated 
as  described  in  the  previous  experiment.  After  standing  six 
weeks,  the  mixture  was  filtered  and  12  g.  arsenofeenzene  ob- 
tained. The  benzene  was  allowed  to  evaporate  spontaneously. 

15  g.  anisic  aldehyde  were  recovered.  The  residue  remaining 
in  the  distilling  flask  was  dissolved  in  hot  alcohol  and  the 
solution  filtered.  On  cooling,  white  prisms,  weight  5 g.  were 
obtained.  The  melting  point,  172-174©,  corresponds  to  hydran- 
isoin , 

4 CH3OC6H4CHO  + 2 C6H5AsHg *2  CE3OC6H4 .CHOH .CHOH .C6H4OCH3 

+ C6E5A s=AsC6Hb 

Ketones.  On  long  standing  or  heating  in  a sealed,  C0S~ 
filled  tube  at  100©,  both  acetone  and  benzophenone  oxidized 
phenylarsine  quantitatively  to  ar senobenzene . This  oxidation 
took  place  in  the  same  manner  in  the  presence  of  cone.  HC1  or 
fused  ZnCls» 

Pyruvic  acid,  diacetyl  and  benzil  reacted  vigorously  in  the 
cold,  the  product  being  invariably  arsenobenzene . Numerous 
experiments  were  made  with  these  ketones  in  an  attempt  to  iso- 
late an  aldehyde-ketone  condensation  product , but  none  could 
be  found.  The  reduction  products  of  the  ketone s, formed  presum- 
ably by  the  action  of  phenylarsine,  were  not  investigated. 


• ; : . 

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. 

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• • 


. 


" 

* 

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39 


Nitrobenzene  » The  action  of  phenylarsine  on  this 


substance  was  investigated  as  a possible  explanation  of  the 


. 


. 


- 


- 40  - 

Reactions  in  which  Hydrogen  Bound  to  Arsenic 
is  Exchanged  for  Halogen* 

Chloral . When  chloral  or  chloral  hydrate  were  allowed  to 
react  with  phenylarsine  a violent  action  took  place.  On  dis- 
t illation  of  the  reaction  mixture  much  excess  chloral  was  re- 
covered,  A colorless  fraction  which  boiled  at  160-182© /70  mm., 
was  identifed  as  C6H5AsClg  by  methods  previously  described  in 
this  paper.  In  Another  experiment  3.5  g.  chloral  were  placed 
in  a COg-filled  Claisen  connected  to  a glass  worm  surrounded 
by  a freezing  mixture.  5 g.  phenylarsine  were  added  drop  by 
drop  through  a cylindrical  dropping  funnel.  The  few  drops  of 
distillate  collected  in  a well-cooled  receiver  were  identified 
as  acetaldehyde  by  boiling  point  and  aldehyde  test.  Some 
arsenobenzene  was  obtained  despite  rigid  exclusion  of  air. 
Doubtless  this  was  formed  by  interaction  of  C6HbAsC1s  and 

CgHgA sRg  » 

3 CsH5AsH2  f 2 CClg.CHO -2  CH3.CHO  3 C6HbAsC12. 

Benzal  chloride.  4 g.  phenylarsine,  4 g.  benzal  chloride, 
1 g.  anhydrous  Na2C03,  25  cc.  xylene  were  refluxed  for  2 hours 
in  a current  of  CO-,,  The  mixture  darkened.  On  cooling,  a 
white  precipitate  formed.  It  was  filtered  off,  extracted  with 
aqueous  Na2C03  to  remove  NaCl  and  traces  of  phenylarsinic  acid, 
and  identified  as  phenylarsine  oxide.  The  apparent  course  of 
the  reaction  was  formation  of  C6H5AsC13w  which  gave  phenylarsine 

(1) 

oxide  by  the  action  of  NasC03. 

(l)  Michaelia,  B.  10,  623  (1877) 


. 

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* 

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- 41  - 

PART  IV 
SUMMARY 

1.  In  the  presence  of  HC1  as  a catalyzer,  one  molecule  of 
phenyl arsine  adds  two  molecules  of  aldehyde  with  the  formation 
of  products  having  the  general  formula,  C6H5As(CHOHR) s . 

3.  These  aldehyde -arsine  compounds  are  remarkably  stable 
toward  water,  acid  and  alkali.  With  most  reagents  the  sub- 
stances  are  indifferent  or  act  like  a mixture  of  phenyl arsine 
and  aldehyde.  Only  in  the  formation  of  addition  compounds  with 
halogen  acid 3 and  certain  metallic  salts,  does  this  new  type 
of  compound  preserve  its  distinctive  character, 

3.  When  heated  with  acetic  anhydride,  CsH5As (CHOHR) E, 
loses  two  molecules  of  alcohol  with  formation  of  a 1,4,3, 6 
dioxdiarsine  ring.  Under  certain  conditions  the  dioxdiarsines 
are  formed  directly  from  phenyl arsine  and  aldehyde.  The  di- 
oxdiarsines resemble  the  first  type  of  condensation  product  in 
mo3t  reactions,  but  do  not  add  halogen  acid, 

4.  From  analogy  with  aniline  it  was  expected  that  phenyl- 
arsine  and  aldehydes  or  ketones  would  give  compounds  of  the 
type,  C6H5As=CHR,  or  C6H5As=CR2,  when  heated  with  a dehydrating 
agent.  Instead,  the  phenylarsine  reduces  the  aldehyde  or 
ketone  to  the  corresponding  alcohol  • 

5.  This  reducing  power  of  phenylarsine  has  suggested  a 
more  correct  mechanism  for  the  interaction  of  aryl  primary 
arsines  with  arsine  oxides,  chlorides,  etc. 


. 


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1 

- 42  - 

6.  In  the  case  of  substances  containing  active  halogen, 
such  as  chloral,  the  only  reaction  is  an  exchange  of  hydrogen 
for  chlorine,  C6H6AsC12  being  formed* 


. ■ 


ACKNOWLEDGEMENT 

The  author  wishes  to  express  his  sincere 
appreciation  of  the  direction  of  Dr.  Roger 
Adams,  which  has  been  responsible  for  the 
success  of  this  work.  Thanks  are  due  to 
Dr.  C.  S.  Marvel  for  many  helpful  aids  in 
experimental  detail. 


. 

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... 

. 


VITA 


I,  Charles  Shattuck  Palmer,  was  born  November  11,  1895, 
at  Champaign,  Illinois,  the  son  of  Arthur  William  Palmer, 
(deceased,  1904),  Director  of  the  Chemical  Laboratory,  Univer- 
sity of  Illinois,  and  his  wife,  Anna  Shattuck  Palmer.  After 
passing  through  the  elementary  and  high  school  of  Urbana, 
Illinois,  I entered  the  University  of  Illinois  in  1913.  Follow- 
ing graduation  in  the  chemistry  course  in  1917  with  the  degree 
of  B.  S.,  I became  Professor  of  Chemistry  in  Greenville  College, 
which  position  I resigned  in  December,  1917,  to  enter  the 
U.  S.  Army.  My  discharge  from  the  army  in  August,  1919,  was 
followed  by  a year  as  Scholar  in  Chemistry,  University  of 
Illinois.  The  degree  of  M.  S.  was  conferred  in  1920.  The 
year  1930-1921  was  spent  as  Fellow  in  Chemistry  (U.  S.  Inter- 
departmental Social  Hygiene  Board) * University  of  Illinois. 


